U.S. patent application number 11/632604 was filed with the patent office on 2007-10-18 for modacrylic shrinkable fiber and method for manufacturing the same.
This patent application is currently assigned to KANEKA CORPORATION. Invention is credited to Toshiaki Ebisu, Kohei Kawamura, Sohei Nishida.
Application Number | 20070243377 11/632604 |
Document ID | / |
Family ID | 35785106 |
Filed Date | 2007-10-18 |
United States Patent
Application |
20070243377 |
Kind Code |
A1 |
Nishida; Sohei ; et
al. |
October 18, 2007 |
Modacrylic Shrinkable Fiber and Method for Manufacturing The
Same
Abstract
A modacrylic shrinkable fiber according to the present invention
is containing a polymer composition obtained by mixing 50 to 99
parts by weight of a polymer (A) containing 40 wt % to 80 wt % of
acrylonitrile, 20 wt % to 60 wt % of a halogen-ontaining monomer
and 0 wt % to 5 wt % of a sulfonic-acid-containing monomer, and 1
to 50 parts by weight of a polymer (B) containing 5 wt % to 70 wt %
of acrylonitrile, 20 wt % to 94 wt % of an acrylic ester and 1 wt %
to 40 wt % of a sulfonic-acid-containing monomer containing a
methallylsulfonic acid or metal salts thereof or amine salts
thereof, in which a total amount of the polymer (A) and the polymer
(B) is 100 parts by weight. In this way, a modacrylic shrinkable
fiber that has a favorable color development property after dyeing
and a high shrinkage ratio even after dyeing is obtained.
Inventors: |
Nishida; Sohei; (Hyogo,
JP) ; Kawamura; Kohei; (Hyogo, JP) ; Ebisu;
Toshiaki; (Hyogo, JP) |
Correspondence
Address: |
HAMRE, SCHUMANN, MUELLER & LARSON, P.C.
P.O. BOX 2902
MINNEAPOLIS
MN
55402-0902
US
|
Assignee: |
KANEKA CORPORATION
Osaka
JP
530-8288
|
Family ID: |
35785106 |
Appl. No.: |
11/632604 |
Filed: |
July 8, 2005 |
PCT Filed: |
July 8, 2005 |
PCT NO: |
PCT/JP05/12695 |
371 Date: |
January 16, 2007 |
Current U.S.
Class: |
428/364 ;
57/362 |
Current CPC
Class: |
Y10T 428/2913 20150115;
Y10T 442/64 20150401; D01F 6/48 20130101; C08F 220/44 20130101;
D01F 6/54 20130101; Y10T 428/2929 20150115; C08F 220/58 20130101;
C08F 228/02 20130101; C08F 220/14 20130101; Y10T 428/2931
20150115 |
Class at
Publication: |
428/364 ;
057/362 |
International
Class: |
D02G 3/00 20060101
D02G003/00; D02G 3/02 20060101 D02G003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 16, 2004 |
JP |
2004-210524 |
Apr 28, 2005 |
JP |
2005-132819 |
Claims
1. A modacrylic shrinkable fiber comprising a polymer composition
obtained by mixing 50 to 99 parts by weight of a polymer (A)
comprising 40 wt % to 80 wt % of acrylonitrile, 20 wt % to 60 wt %
of a halogen-containing monomer and 0 wt % to 5 wt % of a
sulfonic-acid-containing monomer, and 1 to 50 parts by weight of a
polymer (B) comprising 5 wt % to 70 wt % of acrylonitrile, 20 wt %
to 94 wt % of an acrylic ester and 1 wt % to 40 wt % of a
sulfonic-acid-ontaining monomer comprising a methallylsulfonic acid
or metal salts thereof or amine salts thereof; a total amount of
the polymer (A) and the polymer (B) being 100 parts by weight.
2. The modacrylic shrinkable fiber according to claim 1, wherein
the methallylsulfonic acid or the metal salts thereof or the amine
salts thereof in the polymer (B) is sodium methallylsulfonate.
3. The modacrylic shrinkable fiber according to claim 1, which
comprises 0.01 wt % to 10 wt % of sodium methallylsulfonate in the
polymer (B).
4. The modacrylic shrinkable fiber according to claim 1, which
comprises 0.1 wt % to 3 wt % of sodium methallylsulfonate in the
polymer (B).
5. The modacrylic shrinkable fiber according to claim 1, wherein a
relative saturation value at 70.degree. C. or higher is at least
0.8.
6. The modacrylic shrinkable fiber according to claim 1, which is
dyeable at a temperature equal to or lower than 80.degree. C.
7. The modacrylic shrinkable fiber according to claim 1, wherein a
post-dyeing shrinkage ratio of the modacrylic shrinkable fiber
treated in dry heat at 130.degree. C. for 5 minutes is equal to or
larger than 20%.
8. The modacrylic shrinkable fiber according to claim 1, wherein
the polymer (A) and the polymer (B) are incompatible with each
other and have a sea-island structure with the polymer (A) being
the sea and the polymer (B) being the islands.
9. A method for manufacturing a modacrylic shrinkable fiber,
wherein spinning is performed using a spinning solution obtained by
dissolving in acetone 50 to 99 parts by weight of a polymer (A)
comprising 40 wt % to 80 wt % of acrylonitrile, 20 wt % to 60 wt %
of a halogen-containing monomer and 0 wt % to 5 wt % of a
sulfonic-acid-containing monomer, and 1 to 50 parts by weight of a
polymer (B) comprising 5 wt % to 70 wt % of acrylonitrile, 20 wt %
to 94 wt % of an acrylic ester and I wt % to 40 wt % of a
sulfonic-acid-containing monomer comprising a methallylsulfonic
acid or metal salts thereof or amine salts thereof; a total amount
of the polymer (A) and the polymer (B) being 100 parts by
weight.
10. The method for manufacturing a modacrylic shrinkable fiber
according to claim 9, wherein water is dissolved further in the
acetone.
Description
TECHNICAL FIELD
[0001] The present invention relates to a modacrylic
highly-shrinkable fiber that has a favorable color development
property after dyeing and a high shrinkage ratio even after dyeing,
and a method for manufacturing the same.
BACKGROUND ART
[0002] Conventionally, modacrylic fibers have a hand like animal
fur and, owing to such characteristics, have been used for standing
hair products such as toys and clothing. In particular, for the
purpose of providing the feeling of standing hairs and a natural
external appearance, a down hair portion is formed of shrinkable
fibers and a guard hair portion is formed of non-shrinkable fibers
for external appearance in many cases.
[0003] Pile fabrics need to have a good external appearance, so
that the shrinkable fibers also have to have various hues. However,
since the shrinkable fibers shrink due to heat history incurred
during a dyeing process, there currently are only the fibers whose
hues are limited to those colored in a spinning process.
[0004] So far, highly-shrinkable acrylonitrile-based synthetic
fibers have been obtained from a copolymer formed of 30 wt % to 58
wt % of acrylonitrile, 70 wt % to 42 wt % of vinylidene chloride
and vinyl chloride and 0 wt % to 10 wt % of at least one kind of
ethylenic unsaturated monomer (see Patent document 1). However,
according to the knowledge of the inventors of the present
invention, the above-noted shrinkable fibers shrink in dyeing at
70.degree. C. or higher and no longer shrink greatly by the heat in
a tentering process, in which an adhesive is applied to a back
surface of a pile and dried, during pile processing. Further,
although it is possible to suppress the shrinkage by dyeing at a
temperature lower than 70.degree. C. and allow the fibers to shrink
by the heat in the tentering process, sufficient dye-affinity
cannot be achieved. Patent document 1: JP 60(1985)-110911 A
DISCLOSURE OF INVENTION
Problem to be Solved by the Invention
[0005] Accordingly, the present invention solves the
above-described problems of the conventional technology and
achieves a modacrylic shrinkable fiber that has a high shrinkage
ratio even after dyeing and a favorable color development
property.
Means for Solving Problem
[0006] A modacrylic shrinkable fiber according to the present
invention is containing a polymer composition obtained by mixing 50
to 99 parts by weight of a polymer (A) containing 40 wt % to 80 wt
% of acrylonitrile, 20 wt % to 60 wt % of a halogen-ontaining
monomer and 0 wt % to 5 wt % of a sulfonic-acid-containing monomer,
and 1 to 50 parts by weight of a polymer (B) containing 5 wt % to
70 wt % of acrylonitrile, 20 wt % to 94 wt % of an acrylic ester
and 1 wt % to 40 wt % of a sulfonic-acid-containing monomer
containing a methallylsulfonic acid or metal salts thereof or amine
salts thereof, in which a total amount of the polymer (A) and the
polymer (B) is 100 parts by weight.
[0007] In the present invention, it is preferable that the
methallylsulfonic acid or the metal salts thereof or the amine
salts thereof in the polymer (B) is sodium methallylsulfonate.
[0008] Also, it is preferable to contain 0.01 wt % to 10 wt % of
sodium methallylsulfonate in the polymer (B).
[0009] Further, it is preferable to contain 0.1 wt % to 3 wt % of
sodium methallylsulfonate in the polymer (B).
[0010] Moreover, it is preferable that a relative saturation value
at 70.degree. C. is at least 0.8.
[0011] In a method for manufacturing a modacrylic shrinkable fiber
according to the present invention, spinning is performed using a
spinning solution obtained by dissolving in acetone 50 to 99 parts
by weight of a polymer (A) containing 40 wt % to 80 wt % of
acrylonitrile, 20 wt % to 60 wt % of a halogen-containing monomer
and 0 wt % to 5 wt % of a sulfonic-acid-containing monomer, and 1
to 50 parts by weight of a polymer (B) containing 5 wt % to 70 wt %
of acrylonitrile, 20 wt % to 94 wt % of an acrylic ester and 1 wt %
to 40 wt % of a sulfonic-acid-containing monomer containing a
methallylsulfonic acid or metal salts thereof or amine salts
thereof, in which a total amount of the polymer (A) and the polymer
(B) is 100 parts by weight.
[0012] In the manufacturing method according to the present
invention, water may be dissolved further in the acetone. In other
words, it also may be possible to perform spinning using the
spinning solution obtained by dissolving the polymer (A) and the
polymer (B) in a mixed solution of water and acetone.
Effects of the Invention
[0013] In accordance with the present invention, it is possible to
achieve a modacrylic shrinkable fiber that can be dyed and has a
favorable color development property. Also, a modacrylic shrinkable
fiber according to the present invention does not shrink very much
at the time of dyeing and has a high shrinkage ratio even after the
dyeing, thus allowing new product planning for clothing, toys (such
as stuffed toys) and interior decoration.
DESCRIPTION OF THE INVENTION
[0014] In the invention according to Japanese Patent Application
No. 2003-435851, which is not published at the time the present
application is filed, a shrinkable fiber that can be dyed is
obtained by spinning a spinning solution of a polymer composition
obtained by mixing 50 to 99 parts by weight of a polymer (X)
containing at least 40 wt % to 80 wt % of acrylonitrile, 20 wt % to
60 wt % of a halogen-containing monomer and 0 wt % to 5 wt % of a
sulfonic-acid-containing monomer for the purpose of improving a
low-temperature dye-affinity and 1 to 50 parts by weight of a
polymer (Y) containing 5 wt % to 70 wt % of acrylonitrile with a
high dye-affinity and 1 wt % to 40 wt % of other copolymerizable
monomer(s), in which the polymer (X) and the polymer (Y) are
incompatible with each other.
[0015] The invention according to Japanese Patent Application No.
2003-435851 is characterized in that the shrinkable fiber that
shrinks by at least 20% after dyeing is obtained by enhancing the
dye-affinity at low temperatures so as to suppress a shrinkage
ratio during dyeing. However, in the invention of the present
application, it was found that copolymerization of sodium
methallylsulfonate at the time of polymerizing the polymer (Y) with
the polymer (X) made it possible not only to achieve the
characteristics of the invention according to Japanese Patent
Application No. 2003-435851 but also to obtain a modacrylic fiber
that has a high shrinkage ratio even after dyeing and a favorable
color development property by adjusting the degree of
incompatibility between the polymer (X) and the polymer (Y).
[0016] In the polymer (A) of the present invention, it is
preferable to use 40 wt % to 80 wt % of acrylonitrile. When the
acrylonitrile content is less than 40 wt %, the resultant fiber has
low heat resistance. Also, when the acrylonitrile content exceeds
80 wt %, the heat resistance becomes so high that sufficient
dye-affinity and shrinkage ratio cannot be achieved.
[0017] In the polymer (A) of the present invention, the
halogen-containing monomer preferably is selected from vinyl
halides and vinylidene halides represented by vinyl chloride,
vinylidene chloride, vinyl bromide, vinylidene bromide, etc., and
can be one kind or a mixture of two or more kinds of the above. The
content of this halogen-containing monomer in the polymer (A)
preferably is equal to or more than 20 wt % in order to provide the
fiber with a favorable touch without roughness and preferably is
equal to or less than 60 wt % in order to achieve a low
hydrophobicity for sufficient dye-affinity. Thus, 20 wt % to 60 wt
% is preferable.
[0018] In the polymer (A) of the present invention, the
sulfonic-acid-containing monomer preferably is selected from an
allylsulfonic acid, a methallylsulfonic acid, a styrenesulfonic
acid, an isoprenesulfonic acid and a
2-acrylamido-2-methylpropanesulfonic acid, or metal salts thereof
and amine salts thereof, and can be one kind or a mixture of two or
more kinds of the above. It is preferable that the content of the
sulfonic-acid-containing monomer in the polymer (A) of the present
invention is equal to or less than 5 wt % in order to prevent a
decrease in strength due to the generation of voids or
agglutination in the fiber.
[0019] The content of acrylonitrile in the polymer (B) of the
present invention preferably is equal to or more than 5 wt % in
order to maintain the heat resistance of the fiber and preferably
is equal to or less than 70 wt % in order to suppress the
generation of voids in the fiber. Thus, 5 wt % to 70 wt % is
preferable.
[0020] In the polymer (B) of the present invention, the acrylic
ester preferably is methyl acrylate, ethyl acrylate, butyl
acrylate, etc., and these monomers can be used alone or as a
mixture of two or more kinds.
[0021] The content of the acrylic ester in the polymer (B) of the
present invention preferably is equal to or more than 20 wt % in
order to achieve sufficient dye-affinity and preferably is equal to
or less than 94 wt % in order to prevent the generation of voids or
agglutination in the fiber. Thus, 20 wt % to 94 wt % is
preferable.
[0022] In the polymer (B) of the present invention, the
sulfonic-acid-containing monomer preferably is selected from an
allylsulfonic acid, a methallylsulfonic acid, a styrenesulfonic
acid, an isoprenesulfonic acid and a
2-acrylamido-2-methylpropanesulfonic acid, or metal salts thereof
and amine salts thereof, and can be one kind or a mixture of two or
more kinds of the above. Incidentally, among these
sulfonic-acid-containing monomers, "a methallylsulfonic acid or
metal salts thereof or amine salts thereof" are essential
components in the polymer (B) of the present invention and are used
in combination with the other sulfonic-acid-containing monomers.
Further, "a methallylsulfonic acid or metal salts thereof or amine
salts thereof" serving as the essential components in the invention
of the present application preferably is "a methallylsulfonic acid
or metal salts thereof", more preferably is "metal salts of a
methallylsulfonic acid" and particularly preferably is "sodium
methallylsulfonate".
[0023] The content of the sulfonic-acid-containing monomer in the
polymer (B) of the present invention preferably is equal to or more
than 1 wt % in order not to lower the dye-affinity and preferably
is equal to or less than 40 wt % in order to prevent a decrease in
strength due to the generation of voids or agglutination in the
fiber. Thus, 1 wt % to 40 wt % is preferable.
[0024] Since the polymer (A) and the polymer (B) of the present
invention are incompatible with each other, they are considered to
have a so-called sea-island structure, which is a phase separation
structure with the polymer (A), which is present at a higher ratio
in the fiber, being the matrix (sea) and the polymer (B), which is
present at a lower ratio therein, being the domain (islands).
Accordingly, the polymer (B) is not present continuously in the
fiber. Therefore, although the polymer (B) has a low heat
resistance, it does not have a significant influence on the
shrinking behavior. Further, since the polymer (B) contains a
sulfonic group serving as a part to which the dye is bonded and the
acrylic ester having a low softening point, it is possible to
provide the fiber with high dye-affinity.
[0025] In other words, the modacrylic shrinkable fiber according to
the present invention has both of the property of not shrinking
greatly even when dyed at a temperature equal to or lower than
80.degree. C. and the property of being capable of dyeing
modacrylic fibers, which conventionally have been dyeable in deep
colors only at a temperature higher than 80.degree. C., in deep
colors at a temperature equal to or lower than 80.degree. C.,
thereby making it possible to dye modacrylic fibers, which have not
been dyeable conventionally.
[0026] The state of incompatibility referred to in the present
invention can be observed in the spinning solution prepared by
mixing the polymer (A) and the polymer (B). The polymer (A) and the
polymer (B) have a sea-island structure with the polymer (A) being
the sea and the polymer (B) being the islands also in the spinning
solution, and the polymer (B) is present in a granular state due to
phase separation. Further, it is possible to determine the degree
of incompatibility by the grain size of the granular polymer
(B).
[0027] The inventors of the present invention conducted keen
studies and found that there was a relationship between the degree
of incompatibility, namely, the grain size of the polymer (B) in
the spinning solution prepared by mixing the polymer (A) and the
polymer (B) and the color development property.
[0028] The above-noted relationship is as follows: the color
development property is deteriorated with an increase in the grain
size of the polymer (B) in the spinning solution, and the color
development property improves with a decrease in the grain size of
the polymer (B) in the spinning solution.
[0029] In fibers spun out of the spinning solution containing the
polymer (B) with a large grain size, voids are generated easily in
a coagulation step of spinning and tend to cause deterioration of
the color development property. Conversely, in fibers spun out of
the spinning solution containing the polymer (B) with a small grain
size, voids are not generated easily in the coagulation process of
spinning, so that fine fibers are obtained easily and fibers with
favorable color development property are obtained easily.
[0030] However, when the grain size of the polymer (B) in the
spinning solution is too small, fibers become so fine that the dye
cannot infiltrate into the fibers easily. Thus, a dyeing exhaustion
rate tends to lower.
[0031] Moreover, the inventors of the present invention conducted
keen studies and found that it was possible to adjust the grain
size of the polymer (B) in the spinning solution by the
copolymerization amount of sodium methallylsulfonate.
[0032] The grain size of the polymer (B) in the spinning solution
tends to decrease with an increase in the copolymerization amount
of sodium methallylsulfonate, and it tends to increase with a
decrease in the copolymerization amount of sodium
methallylsulfonate.
[0033] More specifically, in the polymer (B) of the present
invention, the content of sodium methallylsulfonate preferably is
0.01 wt % to 10 wt % and particularly preferably is 0.1 wt % to 3
wt %. In terms of the dye-affinity of the fiber, when the content
of sodium methallylsulfonate is 0.01 wt % to 10 wt %, voids are
less likely to be generated in the fiber, so that a fine fiber is
obtained, making it possible to achieve a modacrylic shrinkable
fiber that has favorable dyeing exhaustion rate and color
development property. Furthermore, when the content of sodium
methallylsulfonate is 0.1 wt % to 3 wt %, voids are less likely to
be generated in the fiber, so that a finer fiber is obtained,
making it possible to achieve a modacrylic fiber that has more
favorable dyeing exhaustion rate and color development property.
Also, in terms of the shrinkability of the fiber, when the content
of sodium methallylsulfonate is 0.1 wt % to 3 wt %, voids become
unlikely to be generated in the fiber, which results in favorable
color development property, as well as making it possible to keep a
preferable dispersion size, so that a favorable modacrylic fiber
can be achieved.
[0034] The polymer (A) and the polymer (B) of the present invention
can be obtained using any of known compounds, for example, peroxide
compounds, azo compounds or various redox compounds as a
polymerization initiator by a regular vinyl polymerization method
such as emulsion polymerization, suspension polymerization or
solution polymerization.
[0035] Concerning the mixing ratio of the polymer (A) and the
polymer (B) in the present invention, the ratio of the polymer (B)
less than 1 part by weight with respect to 100 parts by weight of
the total amount of the polymer (A) and the polymer (B) is not
preferable because sufficient dye-affinity cannot be achieved,
whereas the ratio exceeding 50 parts by weight is not preferable
because voids or agglutination are generated in the fiber,
resulting in lower strength and dye-affinity.
[0036] The method for manufacturing a modacrylic shrinkable fiber
according to the present invention includes extrusion from a nozzle
by regular wet spinning in dimethylformamide (DMF) or acetone or
dry spinning, followed by drawing and drying. If necessary, further
drawing and heat treatment also may be carried out. The resultant
fibers are drawn by 1.3 to 4.0 times at 70.degree. C. to
140.degree. C., thereby obtaining shrinkable fibers. Among them,
for the modacrylic shrinkable fiber according to the present
invention, it is preferable that a spinning solution is prepared by
dissolving the polymer (A) and the polymer (B) in acetone. It is
further preferable that a spinning solution is prepared by
dissolving the polymer (A) and the polymer (B) in a mixed solution
of water and acetone. This is preferable because a highly
hydrophilic polymer (B) is dissolved more easily in an
acetone/water system obtained by the addition of water, voids are
less likely to be generated and better dye-affinity and
shrinkability are achieved.
[0037] In the case of dissolving the polymers (A) and (B) in the
mixed solution of water and acetone, the content of water
preferably is 0.01 wt % to 50 wt % and more preferably is 0.1 wt %
to 10 wt % with respect to the spinning solution.
[0038] As this spinning solution, an inorganic and/or organic
pigment such as titanium oxide or coloring pigments, a stabilizing
agent effective in rust prevention, coloring and spinning or
weatherability, or the like also can be used as long as it does not
impair the spinning.
[0039] Incidentally, the color development property referred to in
the present invention indicates how deep the color develops when
fibers are dyed. When the fibers contain only a few voids, the
color develops deeply after dyeing, resulting in a favorable color
development property. On the other hand, in the case where the
fibers contain many voids, a whitish color develops after dyeing,
resulting in a poor color development property. The evaluations
were made as follows.
[0040] The degree of color development property of fibers dyed
using a dye of 0.5% omf Maxilon Red GRL (manufactured by Ciba
Specialty Chemicals.) and a dyeing assistant of 0.5 g/L Ultra MT
#100 (manufactured by Mitejima Chemical Co., Ltd.) at 70.degree. C.
for 60 minutes was evaluated by a sensory test on a scale of A to C
as follows from visual and sensory points of view.
[0041] As a reference sample having a favorable color development
property, fibers obtained by dyeing "Kanecaron (registered
trademark)" SE having a fineness of 3.3 dtex and a length of 38 mm
(manufactured by KANEKA CORPORATION) using the dye of 0.5 % omf
Maxilon Red GRL (manufactured by Ciba Specialty Chemicals.) and the
dyeing assistant of 0.5 g/L Ultra MT #100 (manufactured by Mitejima
Chemical Co., Ltd.) at 100.degree. C. for 60 minutes were used.
[0042] A: color development property equivalent to reference sample
[0043] B: slightly poorer color development property (developing
slightly whitish color) compared with reference sample [0044] C:
poor color development property (developing whitish color) compared
with reference sample
[0045] The post-dyeing shrinkage ratio referred to in the present
invention indicates how much fibers that have been dyed shrink in a
tentering process, and is calculated as follows. After a fiber
having a post-dyeing length of Ldo was treated using a furnace at
130.degree. C. for 5 minutes, the length Ld of the fiber was
measured. Then, the post-dyeing shrinkage ratio was calculated by
the equation below. Post-dyeing shrinkage ratio
(%)=((Ldo-Ld)/Ldo).times.100
[0046] The modacrylic shrinkable fiber according to the present
invention was allowed to shrink in the tentering process during
pile processing. Since the tentering process was conducted in dry
heat at about 130.degree. C., the post-dyeing shrinkage ratio was
determined in dry heat at 130.degree. C.
[0047] When the post-dyeing shrinkage ratio was lower than 20%, the
processed pile fabric had small height difference between the
modacrylic shrinkable fiber according to the present invention and
non-shrinkable raw cotton. Therefore, the height difference was not
emphasized, so that it was not possible to obtain a pile fabric
having natural or fancy external appearance characteristics.
[0048] The relative saturation value referred to in the present
invention indicates a fiber's capability of being dyed, and was
calculated as follows. The fiber was dyed at a predetermined
temperature for 60 minutes using a supersaturated amount of
Malachite Green so as to determine a saturated dyeing capacity, and
then the relative saturation value was calculated from the
saturated dyeing capacity. The saturated dyeing capacity and the
relative saturation value were calculated by the equations below.
Saturated dyeing capacity=((Ao-A)/Ao).times.2.5) [0049] A:
absorbance of dyebath after dyeing (618 nm) [0050] Ao: absorbance
of dyebath before dyeing (618 nm) Relative saturation
value=Saturated dyeing capacity.times.400/463
[0051] Color developed when a modacrylic fiber, for example,
"Kanecaron (registered trademark)" SE having a fineness of 3.3 dtex
and a length of 38 mm (manufactured by KANEKA CORPORATION) exhausts
about 0.5 % omf of the dye of Maxilon Red GRL (manufactured by Ciba
Specialty Chemicals.) is expressed as faint color, color developed
when it exhausts about 1 % omf of the above-noted dye is expressed
as medium deep color, and color developed when it exhausts about 2%
omf of the above-noted dye is expressed as deep color. The
modacrylic shrinkable fiber according to the present invention was
capable of being dyed in deep color at a relative saturation value
of at least 0.8 and thus dyed in almost all colors used in the
market. Therefore, the relative saturation of at least 0.8 is
preferable. Before the description of examples, a method for
evaluating a performance of fibers under test, etc. will be
detailed in the following.
[0052] (1) Production of High Pile
[0053] After shrinkable fibers and non-shrinkable fibers were
blended and subjected to humidity control, slivers were produced
using an opener manufactured by Kodama Tech Co. Ltd. and a carding
machine manufactured by Howa Machinery Ltd. Nagoya. Next, sliver
knitting was carried out with a high pile knitting machine
manufactured by Mayer & Cie., and a pile portion was cut to
align pile lengths with a shirring machine manufactured by Iwakura
Seiki K. K. Subsequently, an acrylic ester-based adhesive was
applied to a back surface of the pile, and the shrinkable fibers
were allowed to shrink while drying the adhesive using a tentering
machine manufactured by HIRANO TECSEED Co., Ltd. at 130.degree. C.
for 5 minutes. Thereafter, polisher finishing and shirring were
carried out with a polisher machine and the shirring machine
manufactured by Iwakura Seiki K. K., thus obtaining a high
pile.
[0054] (2) Evaluation of External Appearance of High Pile
[0055] With respect to the pile fabric with a height difference
produced as in (1) above, the degree of external appearance
characteristics in which the height difference between a long pile
portion and a short pile portion was emphasized was evaluated by a
sensory test on a scale of a to d as follows from visual and
sensory points of view. [0056] a: pile fabric with height
difference having external appearance characteristics in which the
height difference between long pile portion and short pile portion
was emphasized considerably [0057] b: pile fabric with height
difference having external appearance characteristics in which the
height difference between long pile portion and short pile portion
was emphasized [0058] c: pile fabric with height difference in
which the height difference between long pile portion and short
pile portion was not emphasized very much [0059] d: pile fabric
with height difference in which the height difference between long
pile portion and short pile portion hardly was observed
[0060] In general, the external appearance characteristics with
emphasized height difference are provided when the height
difference between the long pile portion and the short pile portion
is equal to or larger than 3 mm, and the external appearance
characteristics with considerably emphasized height difference are
provided when the height difference between them is equal to or
larger than 4 mm. Also, the height difference between these
portions smaller than 3 mm results in the height difference that is
not emphasized very much, and that equal to or smaller than 2 mm
results in substantially no observed height difference.
[0061] In the following, the examples will be described. Parts and
% in the examples respectively mean parts by weight and wt % unless
otherwise specified.
EXAMPLES
Manufacturing Example 1
[0062] In a pressure-resistant polymerization reactor with a
capacity of 20 L, 12000 g of ion-exchange water, 54 g of sodium
lauryl sulfate, 25.8 g of sulfurous acid, 13.2 g of sodium hydrogen
sulfite, 0.06 g of iron sulfate, 294 g of acrylonitrile
(hereinafter, referred to as AN) and 3150 g of vinyl chloride
(hereinafter, referred to as VC) were put and substituted with a
nitrogen atmosphere. The temperature in the reactor was adjusted to
50.degree. C., and 2.1 g of ammonium persulfate serving as an
initiator was placed therein, thus starting polymerization. The
polymerization was performed for 5 hours and 10 minutes while
adding 2526 g of AN, 30 g of sodium styrenesulfonate (hereinafter,
referred to as 3S) and 13.8 g of ammonium persulfate. Thereafter,
unreacted VC was collected, and latex was cleared from the reactor,
followed by salting out, heat treatment, filtering, washing with
water, dewatering and drying, thus obtaining a polymer 1.
[0063] Next, in a pressure-resistant polymerization reactor with a
capacity of 5 L, 1400 g of acetone, 930 g of water, 150 g of AN,
540 g of methyl acrylate (hereinafter, referred to as MA), 300 g of
sodium 2-acrylamido-2-methylpropanesulfonate (hereinafter, referred
to as SAM) and 10 g of sodium methallylsulfonate (hereinafter,
referred to as MX) were put and substituted with a nitrogen
atmosphere. The temperature in the reactor was adjusted to
55.degree. C., and 5 g of 2,2'-azobis(2,4-dimethylvaleronitrile)
serving as an initiator was placed therein, thus starting
polymerization. The polymerization was performed for 16 hours while
adding 10 g of 2,2'-azobis(2,4-dimethylvaleronitrile), followed by
heating to 70.degree. C. and polymerization for 6 hours, thus
obtaining a solution of a polymer 2 having a polymer concentration
of 30 wt %. A spinning solution was prepared by mixing the solution
of the polymer 2 in a solution of the polymer 1, in which the
polymer 1 was dissolved in acetone so as to achieve 30 wt % polymer
1 concentration, such that the weight ratio of polymer 1: polymer
2=96:4. The resultant spinning solution was extruded through a 0.08
mm.phi. spinneret having 8500 holes into a 30 wt % acetone aqueous
solution at 25.degree. C. and further drawn by 2.0 times in a 20 wt
% acetone aqueous solution at 25.degree. C., followed by washing
with water at 60.degree. C. Then, the fibers were dried at
130.degree. C. and further drawn by 1.8 times at 105.degree. C.,
thus obtaining 4.4 dtex drawn fibers.
[0064] Subsequently, the resultant shrinkable fibers were provided
with crimps and cut to 32 mm, and then dyed using the dye of 0.5 %
omf Maxilon Red GRL (manufactured by Ciba Specialty Chemicals.) and
the dyeing assistant of 0.5 g/L Ultra MT #100 (manufactured by
Mitejima Chemical Co., Ltd.) at 70.degree. C. for 60 minutes. Then,
70 wt % of the dyed fibers and 30 wt % of "Kanecaron (registered
trademark)" RCL having a fineness of 12.2 dtex and a length of 44
mm (manufactured by KANEKA CORPORATION), which was a non-shrinkable
raw cotton, were blended so as to produce a high pile. Thereafter,
the pile was cut to have a length of 15 mm in shirring after sliver
knitting, and the pile was cut to have a length of 18 mm after
polisher finishing, thus obtaining a high pile.
Manufacturing Example 2
[0065] In a pressure-resistant polymerization reactor with a
capacity of 5 L, 1400 g of acetone, 930 g of water, 150 g of AN,
545 g of MA, 300 g of SAM and 5 g of MX were put and polymerized by
a method similar to that for the polymer 2 in Manufacturing Example
1, thus obtaining a solution of a polymer 3. A spinning solution
was prepared by mixing the solution of the polymer 3 in the
solution of the polymer 1 obtained in Manufacturing Example 1, in
which the polymer 1 was dissolved in acetone so as to achieve 30 wt
% polymer 1 concentration, such that the weight ratio of polymer 1:
polymer 3=96:4. The resultant spinning solution was spun using a
method similar to that in Manufacturing Example 1, thus obtaining
drawn fibers. From the obtained drawn fibers, a high pile was
produced using a method similar to that in Manufacturing Example
1.
Manufacturing Example 3
[0066] In a pressure-resistant polymerization reactor with a
capacity of 5 L, 1400 g of acetone, 930 g of water, 300 g of AN,
390 g of MA, 300 g of SAM and 10 g of MX were put and polymerized
by a method similar to that for the polymer 2 in Manufacturing
Example 1, thus obtaining a solution of a polymer 4. A spinning
solution was prepared by mixing the solution of the polymer 4 in
the solution of the polymer 1 obtained in Manufacturing Example 1,
in which the polymer 1 was dissolved in acetone so as to achieve 30
wt % polymer 1 concentration, such that the weight ratio of polymer
1: polymer 4=96:4. The resultant spinning solution was spun using a
method similar to that in Manufacturing Example 1, thus obtaining
drawn fibers. From the obtained drawn fibers, a high pile was
produced using a method similar to that in Manufacturing Example
1.
Manufacturing Example 4
[0067] In a pressure-resistant polymerization reactor with a
capacity of 5 L, 1870 g of acetone, 470 g of water, 150 g of AN,
690 g of MA, 150 g of SAM and 10 g of MX were put and polymerized
by a method similar to that for the polymer 2 in Manufacturing
Example 1, thus obtaining a solution of a polymer 5. A spinning
solution was prepared by mixing the solution of the polymer 5 in
the solution of the polymer 1 obtained in Manufacturing Example 1,
in which the polymer 1 was dissolved in acetone so as to achieve 30
wt % polymer 1 concentration, such that the weight ratio of polymer
1: polymer 5=90:10. The resultant spinning solution was spun using
a method similar to that in Manufacturing Example 1, thus obtaining
drawn fibers. From the obtained drawn fibers, a high pile was
produced using a method similar to that in Manufacturing Example
1.
Manufacturing Example 5
[0068] In a pressure-resistant polymerization reactor with a
capacity of 5 L, 1400 g of acetone, 930 g of water, 150 g of AN,
510 g of MA, 300 g of SAM and 40 g of MX were put and polymerized
by a method similar to that for the polymer 2 in Manufacturing
Example 1, thus obtaining a solution of a polymer 6. A spinning
solution was prepared by mixing the solution of the polymer 6 in
the solution of the polymer 1 obtained in Manufacturing Example 1,
in which the polymer 1 was dissolved in acetone so as to achieve 30
wt % polymer 1 concentration, such that the weight ratio of polymer
1: polymer 6=96:4. The resultant spinning solution was spun using a
method similar to that in Manufacturing Example 1, thus obtaining
drawn fibers. From the obtained drawn fibers, a high pile was
produced using a method similar to that in Manufacturing Example
1.
Manufacturing Example 6
[0069] In a pressure-resistant polymerization reactor with a
capacity of 5 L, 1400 g of acetone, 930 g of water, 150 g of AN,
550 g of MA and 300 g of SAM were put and polymerized by a method
similar to that for the polymer 2 in Manufacturing Example 1, thus
obtaining a solution of a polymer 7. A spinning solution was
prepared by mixing the solution of the polymer 7 in the solution of
the polymer 1 obtained in Manufacturing Example 1, in which the
polymer 1 was dissolved in acetone so as to achieve 30 wt % polymer
1 concentration, such that the weight ratio of polymer 1 : polymer
7=96:4. The resultant spinning solution was spun using a method
similar to that in Manufacturing Example 1, thus obtaining drawn
fibers. From the obtained drawn fibers, a high pile was produced
using a method similar to that in Manufacturing Example 1.
[0070] Table 1 shows the methods for manufacturing the fibers
obtained in Manufacturing Examples 1 to 6.
[0071] [Table 1] TABLE-US-00001 TABLE 1 Blend composition Base
polymer composition Blend polymer composition Blend polymer/Base
polymer Manufacturing Ex. 1 Polymer 1
AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 2
AN.sup.15-MA.sup.54-SAM.sup.30-MX.sup.1 96/4 Manufacturing Ex. 2
Polymer 1 AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 3
AN.sup.15-MA.sup.54.5-SAM.sup.30-MX.sup.0.5 96/4 Manufacturing Ex.
3 Polymer 1 AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 4
AN.sup.30-MA.sup.39-SAM.sup.30-MX.sup.1 96/4 Manufacturing Ex. 4
Polymer 1 AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 5
AN.sup.15-MA.sup.69-SAM.sup.15-MX.sup.1 90/10 Manufacturing Ex. 5
Polymer 1 AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 6
AN.sup.15-MA.sup.51-SAM.sup.30-MX.sup.4 96/4 Manufacturing Ex. 6
Polymer 1 AN.sup.47-VC.sup.52.5-3S.sup.0.5 Polymer 7
AN.sup.15-MA.sup.55-SAM.sup.30 96/4 (Note) Numerical values
indicate wt %. AN: acrylonitrile VC: vinyl chloride 3S: sodium
styrenesulfonate MA: methyl acrylate SAM: sodium
2-acrylamido-2-methylpropanesulfonate MX: sodium
methallylsulfonate
Examples 1 to 4
[0072] Table 2 shows the color development property, relative
saturation value, post-dyeing shrinkage ratio and evaluation of
pile external appearance of the shrinkable fibers obtained in
Manufacturing Examples 1 to 4.
[0073] [Table 2] TABLE-US-00002 TABLE 2 Color Relative Post-dyeing
Manufacturing development saturation value shrinkage ratio dyed
Evaluation of high pile method property dyed at 70.degree. C. at
70.degree. C. (%) external appearance Ex. 1 Manufacturing Ex. 1 A
0.9 31 a Ex. 2 Manufacturing Ex. 2 A 0.9 32 a Ex. 3 Manufacturing
Ex. 3 A 0.9 31 a Ex. 4 Manufacturing Ex. 4 A 0.9 31 a Ex. 5
Manufacturing Ex. 5 A 0.4 32 a Comp. Ex. 1 Manufacturing Ex. 6 C
0.9 31 a
[0074] Shrinkable fibers respectively obtained by mixing the
polymers 2 to 5 containing 0.1 wt % to 3 wt % of sodium
methallylsulfonate followed by spinning had a favorable color
development property and had a relative saturation value of at
least 0.8, allowing dyeing into any color from faint colors to deep
colors. Furthermore, it was possible to obtain the high pile having
a post-dyeing shrinkage ratio of equal to or larger than 20% and
external appearance characteristics in which the height difference
between the long pile portion and the short pile portion was
emphasized.
Example 5
[0075] Table 2 shows the color development property, relative
saturation value, post-dyeing shrinkage ratio and evaluation of
pile external appearance of the shrinkable fibers obtained in
Manufacturing Example 5. Shrinkable fibers obtained by mixing the
polymer 6 containing 3% of sodium methallylsulfonate followed by
spinning made it possible to obtain the high pile having a
post-dyeing shrinkage ratio of equal to or larger than 20 wt % and
external appearance characteristics in which the height difference
between the long pile portion and the short pile portion was
emphasized. However, although the color development property was
favorable, the relative saturation value was smaller than 0.8,
which did not allow dyeing into deep colors.
Comparative Example 1
[0076] Table 2 shows the color development property, relative
saturation value, post-dyeing shrinkage ratio and evaluation of
pile external appearance of the shrinkable fibers obtained in
Manufacturing Example 6. Shrinkable fibers obtained by mixing the
polymer 7 containing no sodium methallylsulfonate followed by
spinning made it possible to obtain the high pile having a
post-dyeing shrinkage ratio of equal to or larger than 20% and
external appearance characteristics in which the height difference
between the long pile portion and the short pile portion was
emphasized. However, although the relative saturation value was at
least 0.8, which allowed dye exhaustion, the color development
property was poor, resulting in a whitish color.
INDUSTRIAL APPLICABILITY
[0077] The modacrylic shrinkable fiber according to the present
invention does not shrink very much at the time of dyeing and has a
high shrinkage ratio even after the dyeing, and consequently,
allows new product planning for a wide range of products such as
clothing, toys (stuffed toys or the like) and interior
decoration.
* * * * *